CN108103769A - A kind of aramid fiber surface treatment fluid and preparation method thereof - Google Patents

A kind of aramid fiber surface treatment fluid and preparation method thereof Download PDF

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Publication number
CN108103769A
CN108103769A CN201810039367.2A CN201810039367A CN108103769A CN 108103769 A CN108103769 A CN 108103769A CN 201810039367 A CN201810039367 A CN 201810039367A CN 108103769 A CN108103769 A CN 108103769A
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solution
aramid fiber
parts
rubber
water
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CN108103769B (en
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陈刚
王东彬
高殿飞
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YANTAI TAYHO ADVANCED MATERIALS CO Ltd
Taihe Engineering Materials Co Ltd
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YANTAI TAYHO ADVANCED MATERIALS CO Ltd
Taihe Engineering Materials Co Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55Epoxy resins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/60Ammonia as a gas or in solution
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12Aldehydes; Ketones
    • D06M13/127Mono-aldehydes, e.g. formaldehyde; Monoketones
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395Isocyanates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41Phenol-aldehyde or phenol-ketone resins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • D06M2101/36Aromatic polyamides

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a kind of aramid fiber surface treatment fluid, the prescription for the treatment of liquid according to mass fraction meter is as follows:Preprocessing solution:Toluene 160 ~ 180, poly methylene poly phenyl poly isocyanate 16 ~ 18, epoxy resin 4 ~ 6, coumarone indene resin 0 ~ 4, chlorinated natural rubber 0 ~ 2, nitrile rubber 0 ~ 3;Reprocess solution:Deionized water 180 ~ 200, water-soluble resorcinol formaldehyde resin 10 ~ 15,25% ~ 30% ammonium hydroxide 10 ~ 15, butadiene-vinylpyridine copylymer latex 180 ~ 200,36% ~ 40% formaldehyde 10 ~ 13.Aramid fiber is impregnated using this treatment fluid, surface property is effectively improved, and improves the bond properties of aramid fiber.

Description

A kind of aramid fiber surface treatment fluid and preparation method thereof
Technical field
The present invention relates to tire or conveyer belt production technical fields, and in particular to a kind of aramid fiber surface treatment fluid and its Preparation method.
Background technology
Aramid fiber is succeeded in developing from the sixties in last century by du pont company, and in the commercialization seventies, due to it The advantages that high intensity itself, high-modulus, is applied to the fields such as bullet-proof vest, fire-entry suit, aerospace, framework material.But Aramid fiber strand arranged regular and active function groups are few, causes its bond properties between basis material very poor, greatly Ground limits its application in terms of framework material.
Aramid fiber be it is a kind of formed by rigid molecule chain, there are high intensity, high-modulus, high temperature resistant and the deformation superiority such as small The new special High performance industrial fiber of energy.However aramid fiber has unique " Pi Yixin " structure, core leans on hydrogen by many The rodlike molecule of key connection is formed, and epidermis is formed by the high rigid molecule chain of crystallinity along fiber axial alignment, and thickness is about The 1%-40% of only entire fibre diameter.Again since aramid fiber molecular structure belongs to phenyl rigid molecule, phenyl ring is to phthalein amine official Hydrogen atom on rolling into a ball has shielding action so that fiber surface lacks activity, and hardly possible forms chemical covalent bonds, and benzene on interface The steric effect of ring, is hardly formed hydrogen bond so that surface lacks chemical active radical, and surface is smooth, and interface adhesion is poor, makes Composite material interlayer shear strength is low.These situations limit the performance of material superiority, excellent in order to give full play to aramid fiber Mechanical property, it is necessary to be modified processing to aramid fiber surface, to improve the interface bonding state of aramid fiber enhancing composite material.
At present, aramid fiber surface modified method mainly has:Plasma surface modification technology, ultrasonic wave force infiltration skill Art, gamma radiation method, chemical grafting treated method etc..
Plasma surface modification:The radical reaction for triggering aramid fiber using plasma carries out.By plasma Trigger the free radical generated followed by reactions such as cracking, radical transfer, oxidation, disproportionation and lotus root conjunctions.
Ultrasonic wave forces imbibition technique:Mainly using ultrasound cause in a liquid generated during the rupture of bubble high temperature, High pressure and local shock effect cause the variation of thermoplastic resin-impregnated fibers.
Gamma radiation method:Surface grafting and fibrous inside fento cross-linking reaction are carried out to aramid fiber using mono- rays of Y, It is that a kind of new improved technology, this method are not required in recent years so as to improve the method for fiber bodies intensity and its wetability Catalyst or initiator can be reacted at normal temperatures, be a kind of rising modification technology.
Chemical grafting treated method:Chemical modification method is using chemical reaction, and reactive group is introduced in fiber surface, So as to generate covalent bond with matrix compound tense, increase the interface performance of material.Its method is generally divided into surface etch, coupling agent Modified and surface grafting.
But when above method is modified, there are following problems:Investment is big, and reaction condition is high or needs the reaction participated in Object is more, and consersion unit is more, and interfacial bonding property is poor.
The present invention is on the basis of forefathers study, and by changing the processing method of aramid fiber, reaches and improves aramid fiber fibre The bond properties of dimension, the purpose for widening its application field.
The content of the invention
The object of the present invention is to provide a kind of aramid fiber surface treatment fluids and preparation method thereof, are soaked using this treatment fluid Stain aramid fiber, surface property are effectively improved, and improve the bond properties of aramid fiber.
In order to achieve the above object, the present invention realizes by the following technical solutions:
A kind of aramid fiber surface treatment fluid, the prescription for the treatment of liquid according to mass fraction meter are as follows:
Preprocessing solution:Toluene 160 ~ 180, poly methylene poly phenyl poly isocyanate 16 ~ 18, epoxy resin 4 ~ 6, coumarone Resin 0 ~ 4, chlorinated natural rubber 0 ~ 2, nitrile rubber 0 ~ 3;
Reprocess solution:Deionized water 180 ~ 200, water-soluble resorcinol-formaldehyde resin 10 ~ 15,25% ~ 30% ammonium hydroxide 10 ~ 15, butadiene-vinylpyridine copylymer latex 180 ~ 200,36% ~ 40% formaldehyde 10 ~ 13.
The present invention also provides the preparation method of above-mentioned aramid fiber surface treatment fluid and aramid fiber surface treatment process, Include the following steps:
S1:By coumarone indene resin in mortar crushed into powder shape, nitrile rubber is ground into the rubber of 3-5mm after over-mastication Particle;
S2:Coumarone indene resin, nitrile rubber, chlorinated natural rubber after crushing is added in toluene, configures the mixing of three The mother liquor of solution, placing 2-3h at ambient temperature makes three be dissolved completely in toluene;
S3:It treats that coumarone indene resin, nitrile rubber, chlorinated natural rubber are dissolved completely in toluene, weighs polymethylene polyphenyl Polyisocyanates, epoxy resin are added in above-mentioned mother liquor, and aramid fiber surface pretreatment fluid is made after being sufficiently stirred;
S4:According to reprocessing solution formula, each component of precise prepares the solution of three systems, is respectively No. 1 molten first Liquid:30 ~ 35 parts of deionized water is weighed first as solvent, then weigh water-soluble 10 ~ 15 parts of resorcinol-formaldehyde resin, 25% ~ 30% 5 ~ 8 parts of ammonium hydroxide is dispersed in water, and being sufficiently stirred makes solution be uniformly dispersed;No. 2 solution:Weigh first deionized water 120 ~ 130 parts be used as solvent, then weigh 180 ~ 200 parts of butadiene-vinylpyridine copylymer latex, 5 ~ 7 parts of 25% ~ 30% ammonium hydroxide is dispersed in water, being sufficiently stirred makes Solution is uniformly dispersed;No. 3 solution:30 ~ 35 parts of deionized water is weighed first, then is weighed 10 ~ 13 parts of 36% ~ 40% formaldehyde and be dispersed in In water, being sufficiently stirred makes solution be uniformly dispersed;
S5:Successively No. 1 solution in S4 and No. 3 solution are slowly added into No. 2 solution, it is stirring while adding, after mixing Curing 12h is reused at ambient temperature;
S6:First using surface preparation solution impregnate aramid fiber 10s ~ 20s, then 120s dry prior to 150 DEG C ~ 160 DEG C ~ 200s reacts 120s ~ 200s under the conditions of 210 DEG C ~ 230 DEG C, reuses surface reprocessing solution and is dipped through pretreatment Aramid fiber 20s ~ 30s, then prior to 140 DEG C ~ 150 DEG C under the conditions of dry 120s ~ 200s, under the conditions of 200 DEG C ~ 220 DEG C React 120s ~ 200s.
Using poly methylene poly phenyl poly isocyanate in aramid fiber surface treatment fluid provided by the invention, in molecule Isocyanate group chemical reaction can occur with the groups such as amino, the imino group on aramid fiber surface or form hydrogen bond, Improve the interaction between boundary layer and aramid fiber surface.
Coumarone indene resin is added in surface treatment liquid, play an important role of to be plasticized and is viscosified, it, can be in Vulcanization Process of Rubber The rubber molecular chain being plasticized at adhesive interface makes rubber molecular chain be spread to fiber surface, improves wellability of the rubber to fiber.
Chlorinated natural rubber and nitrile rubber are added in surface processing solution, there are thickening, two kinds of one sides of rubber The poly methylene poly phenyl poly isocyanate that face can be pretreated in solution cures crosslinking, on the other hand can be molten with reprocessing Latex in liquid mutually generates the co-vulcanization of rubber.
Water-soluble resorcinol-formaldehyde resin is added in surface processing solution, for methylene receptor, surface processing solution In be also added into formalin, be methylene methylene donor, the two can improve the modulus of boundary layer after curing.
Butadiene-vinylpyridine copylymer latex is added in surface processing solution, can be complexed with resorcinol-formaldehyde resin, and and rubber Co-vulcanization occurs for strand.
Specific embodiment
Technical scheme is described in detail below by specific embodiment, but the scope of the present invention is not It is limited to these embodiments.
Embodiment 1:A kind of aramid fiber surface treatment fluid, prescription for the treatment of liquid in parts by weight are as follows:(1)Pre- place Manage solution:Toluene 180, poly methylene poly phenyl poly isocyanate 16, epoxy resin 4, coumarone indene resin 2, chlorinated natural Rubber 1, nitrile rubber 1;(2)Reprocess solution:Deionized water 194, water-soluble resorcinol-formaldehyde resin 11,25% ~ 30% ammonium hydroxide 9, butadiene-vinylpyridine copylymer latex 190,36% ~ 40% formalin 12.
The present invention also provides the preparation methods of above-mentioned aramid fiber surface treatment fluid, include the following steps:
S1:By coumarone indene resin in mortar crushed into powder shape, nitrile rubber is ground into the rubber of 3-5mm after over-mastication Particle;
S2:Coumarone indene resin, nitrile rubber, chlorinated natural rubber after crushing is added in toluene, configures the mixing of three The mother liquor of solution, placing 2-3h at ambient temperature makes three be dissolved completely in toluene;
S3:It treats that coumarone indene resin, nitrile rubber, chlorinated natural rubber are dissolved completely in toluene, weighs polymethylene polyphenyl Polyisocyanates, epoxy resin are added in above-mentioned mother liquor, and aramid fiber surface pretreatment fluid is made after being sufficiently stirred;
S4:According to reprocessing solution formula, each component of precise prepares the solution of three systems, is respectively No. 1 molten first Liquid:35 parts of deionized water is weighed first as solvent, then weighs water-soluble 11 parts of resorcinol-formaldehyde resin, 25% ~ 30% ammonium hydroxide 5 parts are dispersed in water, and being sufficiently stirred makes solution be uniformly dispersed;No. 2 solution:130 parts of deionized water is weighed first as solvent, then Weigh 190 parts of butadiene-vinylpyridine copylymer latex, 2 parts points of 25% ~ 30% ammonium hydroxide is spread in water, being sufficiently stirred makes solution be uniformly dispersed;No. 3 solution: 29 parts of deionized water is weighed first, then weighs 12 parts points of 36% ~ 40% formalin and spreads in water, and being sufficiently stirred disperses solution Uniformly;
S5:Successively No. 1 solution in S4 and No. 3 solution are slowly added into No. 2 solution, it is stirring while adding, after mixing Curing more than 12h is reused at ambient temperature;
S6:Aramid fiber 10s ~ 20s is impregnated using surface preparation solution first, then prior to 160 DEG C dry 120s, after React 180s under the conditions of 210 DEG C, reuse surface reprocessing solution and be dipped through the aramid fiber 20s of pretreatment, then prior to Dry 150s, reacts 120s under the conditions of 220 DEG C under the conditions of 140 DEG C.
With open mill by rubber plastic steelmaking, bottom sheet, cutting.Rubber, aramid fiber is put into mold together with treated, uses Vulcanizing press press cure.Conditions of vulcanization is:160 DEG C, 10MPa, 20min.Embedding length of the aramid fiber in rubber is 10mm。
According to standard GB/T/T 2942-1991, on universal testing machine vulcanized test specimens are carried out with T extraction tests, test Speed is 125mm/min.Visual observations extract the binding efficiency of aramid fiber surface out.A factory of tyre company is used in experiment The natural rubber that family provides, holder aperture used in extraction test are 6mm.It is calm and peaceful new for Yantai to test the aramid fiber used The untreated para-aramid fiber of material limited company production.
The bonding of the aramid fiber and natural rubber that are handled using aramid fiber surface treatment fluid provided by the invention is extracted out Power is 189N, binding efficiency 40%;It is 65N to be not impregnated with the aramid fiber of processing and the bonding extraction force of natural rubber, and binding efficiency is 0%。
Embodiment 2:A kind of aramid fiber surface treatment fluid, prescription for the treatment of liquid in parts by weight are as follows:(1)Pre- place Manage solution:Toluene 160, poly methylene poly phenyl poly isocyanate 15, epoxy resin 6, coumarone indene resin 0.1, butyronitrile rubber Glue 0.2;(2)Reprocess solution:Deionized water 194, water-soluble resorcinol-formaldehyde resin 11,25% ~ 30% ammonium hydroxide 9, fourth Pyrrole latex 190,36% ~ 40% formalin 12.
The present invention also provides the preparation methods of above-mentioned aramid fiber surface treatment fluid, include the following steps:
S1:By coumarone indene resin in mortar crushed into powder shape, nitrile rubber is ground into the rubber of 3-5mm after over-mastication Particle;
S2:Coumarone indene resin, nitrile rubber, chlorinated natural rubber after crushing is added in toluene, configures the mixing of three The mother liquor of solution, placing 2-3h at ambient temperature makes three be dissolved completely in toluene;
S3:It treats that coumarone indene resin, nitrile rubber, chlorinated natural rubber are dissolved completely in toluene, weighs polymethylene polyphenyl Polyisocyanates, epoxy resin are added in above-mentioned mother liquor, and aramid fiber surface pretreatment fluid is made after being sufficiently stirred;
S4:According to reprocessing solution formula, each component of precise prepares the solution of three systems, is respectively No. 1 molten first Liquid:35 parts of deionized water is weighed first as solvent, then weighs water-soluble 15 parts of resorcinol-formaldehyde resin, 25% ~ 30% ammonium hydroxide 8 parts are dispersed in water, and being sufficiently stirred makes solution be uniformly dispersed;No. 2 solution:120 parts of deionized water is weighed first as solvent, then Weigh 200 parts of butadiene-vinylpyridine copylymer latex, 5 parts points of 25% ~ 30% ammonium hydroxide is spread in water, being sufficiently stirred makes solution be uniformly dispersed;No. 3 solution:It is first 30 parts of deionized water is first weighed, then weighs 13 parts points of 36% ~ 40% formalin and spreads in water, being sufficiently stirred makes solution disperse It is even;
S5:Successively No. 1 solution in S4 and No. 3 solution are slowly added into No. 2 solution, it is stirring while adding, after mixing Curing more than 12h is reused at ambient temperature;
S6:Aramid fiber 20s is impregnated using surface preparation solution first, then prior to 160 DEG C dry 200s, after 210 DEG C Under the conditions of react 120s, reuse surface reprocessing solution and be dipped through the aramid fiber 30s of pretreatment, then prior to 140 DEG C Under the conditions of dry 200s, react 200s under the conditions of 220 DEG C.
With open mill by rubber plastic steelmaking, bottom sheet, cutting.Rubber, aramid fiber is put into mold together with treated, uses Vulcanizing press press cure.Conditions of vulcanization is:160 DEG C, 10MPa, 20min.Embedding length of the aramid fiber in rubber is 10mm。
According to standard GB/T/T 2942-1991, on universal testing machine vulcanized test specimens are carried out with T extraction tests, test Speed is 125mm/min.Visual observations extract the binding efficiency of aramid fiber surface out.A factory of tyre company is used in experiment The natural rubber that family provides, holder aperture used in extraction test are 6mm.It is calm and peaceful new for Yantai to test the aramid fiber used The untreated para-aramid fiber of material limited company production.
The bonding of the aramid fiber and natural rubber that are handled using aramid fiber surface treatment fluid provided by the invention is extracted out Power is 189N, binding efficiency 45%;It is 68N to be not impregnated with the aramid fiber of processing and the bonding extraction force of natural rubber, and binding efficiency is 0%。
Embodiment 3:A kind of aramid fiber surface treatment fluid, prescription for the treatment of liquid in parts by weight are as follows:(1)Pre- place Manage solution:Toluene 170, poly methylene poly phenyl poly isocyanate 18, epoxy resin 5, coumarone indene resin 2, chlorinated natural Rubber 1, nitrile rubber 1;(2)Reprocess solution:Deionized water 194, water-soluble resorcinol-formaldehyde resin 12,25% ~ 30% ammonium hydroxide 10, butadiene-vinylpyridine copylymer latex 180,36% ~ 40% formalin 10.
The present invention also provides the preparation methods of above-mentioned aramid fiber surface treatment fluid, include the following steps:
S1:By coumarone indene resin in mortar crushed into powder shape, nitrile rubber is ground into the rubber of 3-5mm after over-mastication Particle;
S2:Coumarone indene resin, nitrile rubber, chlorinated natural rubber after crushing is added in toluene, configures the mixing of three The mother liquor of solution, placing 2-3h at ambient temperature makes three be dissolved completely in toluene;
S3:It treats that coumarone indene resin, nitrile rubber, chlorinated natural rubber are dissolved completely in toluene, weighs polymethylene polyphenyl Polyisocyanates, epoxy resin are added in above-mentioned mother liquor, and aramid fiber surface pretreatment fluid is made after being sufficiently stirred;
S4:According to reprocessing solution formula, each component of precise prepares the solution of three systems, is respectively No. 1 molten first Liquid:30 parts of deionized water is weighed first as solvent, then weighs water-soluble 12 parts of resorcinol-formaldehyde resin, 25% ~ 30% ammonia 5 parts of water is dispersed in water, and being sufficiently stirred makes solution be uniformly dispersed;No. 2 solution:It is molten that 130 parts of conducts of deionized water are weighed first Agent, then weigh butadiene-vinylpyridine copylymer latex(VP latex)180 parts, 5 parts points of 25% ~ 30% ammonium hydroxide spread in water, being sufficiently stirred disperses solution Uniformly;No. 3 solution:34 parts of deionized water is weighed first, then weighs 10 parts points of 36% ~ 40% formaldehyde and spreads in water, is sufficiently stirred Solution is made to be uniformly dispersed;
S5:Successively No. 1 solution in S4 and No. 3 solution are slowly added into No. 2 solution, it is stirring while adding, after mixing Curing 12h is reused at ambient temperature;
S6:Aramid fiber 15s is impregnated using surface preparation solution first, then prior to 160 DEG C dry 150, after 220 DEG C of items 120s is reacted under part, reuses the aramid fiber 20s that surface reprocessing solution is dipped through pretreatment, then prior to 145 DEG C items Dry 120s, reacts 120s under the conditions of 210 DEG C under part.
Ethylene propylene diene rubber is plasticated with open mill, bottom sheet, cutting.Rubber, aramid fiber is put into together with treated Mold, with vulcanizing press press cure.Conditions of vulcanization is:160 DEG C, 10MPa, 35min.Embedding of the aramid fiber in rubber Length is 10mm.
According to standard GB/T/T 2942-1991, on universal testing machine vulcanized test specimens are carried out with T extraction tests, extraction Speed is 125mm/min.The binding efficiency of visual observations aramid fiber surface.Three provided in experiment using a conveyer belt producer First EP rubbers, holder aperture used in extraction test are 6mm.It is the calm and peaceful green wood share in Yantai to test the aramid fiber used The untreated para-aramid fiber that Co., Ltd provides.
The aramid fiber and the bonding extraction force of ethylene propylene diene rubber prepared using surface treatment liquid provided by the invention be 238N, rate of adding are 60%;It is 70N to be not impregnated with the aramid fiber of processing and the bonding extraction force of ethylene propylene diene rubber, and additional rate is 0%。
Present invention uses the dipping systems different from traditional maceration extract to handle aramid fiber, and tool is added in maceration extract There are the coumarone indene resin of plasticising and tackifying effect and chlorinated natural rubber and nitrile rubber with Efficient Adhesive Promotion.And with as follows Advantageous effect:
(1)Coumarone indene resin, chlorinated natural rubber, nitrile rubber are added in maceration extract, improves bonding force.
(2)Poly methylene poly phenyl poly isocyanate is added in maceration extract, it can be with activated fiber surface.
(3)Using two-part impregnation technology:Surface preparation and surface reprocessing, and each segment process is all complete by three steps Into, it respectively first impregnates, re-dry, it is rear to react.
(4)Reprocessing solution is made of three parts, is respectively No. 1 solution:Deionized water 30 ~ 35, water-soluble isophthalic two Resinox 10 ~ 15,25% ~ 30% ammonium hydroxide 5 ~ 8;No. 2 solution:Deionized water 120 ~ 130, butadiene-vinylpyridine copylymer latex 180 ~ 200, 25% ~ 30% ammonium hydroxide 5 ~ 7;No. 3 solution:Deionized water 30 ~ 35,36% ~ 40% formalin 10 ~ 13.Three parts solution has been prepared No. 1 solution and No. 3 solution are added in No. 2 solution respectively into rear, being sealed more than 12h after being sufficiently stirred reuses.
The specific embodiment of the present invention is described above, but these explanations are not considered as limiting the present invention's Scope, protection scope of the present invention are limited by appended claims, any change on the basis of the claims in the present invention All it is protection scope of the present invention.

Claims (5)

1. a kind of aramid fiber surface treatment fluid, it is characterised in that:Including pretreatment fluid and reprocessing liquid, the pretreatment fluid bag Include toluene, poly methylene poly phenyl poly isocyanate, epoxy resin, coumarone indene resin, chlorinated natural rubber and nitrile rubber; The reprocessing liquid includes deionized water, water-soluble resorcinol-formaldehyde resin, ammonium hydroxide, butadiene-vinylpyridine copylymer latex and formaldehyde.
2. aramid fiber surface treatment fluid according to claim 1, it is characterised in that:The mass fraction of each component is
Toluene 160 ~ 180
Poly methylene poly phenyl poly isocyanate 16 ~ 18
Epoxy resin 4 ~ 6
Coumarone indene resin 0 ~ 4
Chlorinated natural rubber 0 ~ 2
Nitrile rubber 0 ~ 3
Deionized water 180 ~ 200
Water-soluble resorcinol-formaldehyde resin 10 ~ 15,
25% ~ 30% ammonium hydroxide 10 ~ 15
Butadiene-vinylpyridine copylymer latex 180 ~ 200
36% ~ 40% formaldehyde 10 ~ 13.
3. a kind of preparation method of the aramid fiber surface treatment fluid described in claim 1 or 2, it is characterised in that:Including as follows Step:
S1:By coumarone indene resin in mortar crushed into powder shape, nitrile rubber is ground into rubber grain after over-mastication;
S2:Coumarone indene resin, nitrile rubber, chlorinated natural rubber after crushing is added in toluene, configures the mixing of three The mother liquor of solution, placing 2-3h at ambient temperature makes three be dissolved completely in toluene;
S3:It treats that coumarone indene resin, nitrile rubber, chlorinated natural rubber are dissolved completely in toluene, weighs polymethylene polyphenyl Polyisocyanates, epoxy resin are added in above-mentioned mother liquor, and aramid fiber surface pretreatment fluid is made after being sufficiently stirred;
S4:According to reprocessing solution formula, each component of precise prepares the solution of three systems, is respectively No. 1 molten first Liquid:30 ~ 35 parts of deionized water is weighed first as solvent, then weigh water-soluble 10 ~ 15 parts of resorcinol-formaldehyde resin, 25% ~ 30% 5 ~ 8 parts of ammonium hydroxide is dispersed in water, and being sufficiently stirred makes solution be uniformly dispersed;No. 2 solution:Weigh first deionized water 120 ~ 130 parts be used as solvent, then weigh 180 ~ 200 parts of butadiene-vinylpyridine copylymer latex, 5 ~ 7 parts of 25% ~ 30% ammonium hydroxide is dispersed in water, being sufficiently stirred makes Solution is uniformly dispersed;No. 3 solution:30 ~ 35 parts of deionized water is weighed first, then is weighed 10 ~ 13 parts of 36% ~ 40% formaldehyde and be dispersed in In water, being sufficiently stirred makes solution be uniformly dispersed;
S5:Successively No. 1 solution in S4 and No. 3 solution are slowly added into No. 2 solution, it is stirring while adding, after mixing Curing 12h is reused at ambient temperature;
S6:Aramid fiber is impregnated using surface preparation solution first, drying is then dried, after 210 DEG C ~ 230 DEG C items It is reacted under part, reuses the aramid fiber that surface reprocessing solution is dipped through pretreatment, then prior to 140 DEG C ~ 150 DEG C conditions Lower drying is reacted under the conditions of 200 DEG C ~ 220 DEG C.
4. the preparation method of aramid fiber surface treatment fluid according to claim 3, it is characterised in that:By butyronitrile rubber in S1 Glue is ground into the rubber grain of 3-5mm after over-mastication.
5. the preparation method of aramid fiber surface treatment fluid according to claim 3, it is characterised in that:In S6, use first Surface preparation solution impregnates aramid fiber 10s ~ 20s, then prior to 150 DEG C ~ 160 DEG C dry 120s ~ 200s, after 210 DEG C ~ 120s ~ 200s is reacted under the conditions of 230 DEG C, reuses aramid fiber 20s ~ 30s that surface reprocessing solution is dipped through pretreatment, Then prior to 140 DEG C ~ 150 DEG C under the conditions of dry 120s ~ 200s, 120s ~ 200s is reacted under the conditions of 200 DEG C ~ 220 DEG C.
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CN115975266B (en) * 2022-12-27 2024-05-14 宁国市赛科思橡胶有限公司 Natural/butadiene rubber compound with high extraction force and high flexibility and preparation method thereof

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